JP2006265171A - Perfume composition and new method for improving or enhancing fragrant character of pastille - Google Patents
Perfume composition and new method for improving or enhancing fragrant character of pastille Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title claims description 13
- 239000002304 perfume Substances 0.000 title abstract description 3
- 235000010603 pastilles Nutrition 0.000 title 1
- 239000003205 fragrance Substances 0.000 claims abstract description 50
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000002688 persistence Effects 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- LLWGDNREPDWSRL-ACCUITESSA-N (2e)-cyclopentadec-2-en-1-one Chemical compound O=C/1CCCCCCCCCCCC\C=C\1 LLWGDNREPDWSRL-ACCUITESSA-N 0.000 claims abstract description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011541 reaction mixture Substances 0.000 claims abstract 2
- KEPJZBFFLDRKSF-UHFFFAOYSA-M trimethylsulfoxonium bromide Chemical compound [Br-].C[S+](C)(C)=O KEPJZBFFLDRKSF-UHFFFAOYSA-M 0.000 claims description 6
- LLWGDNREPDWSRL-UHFFFAOYSA-N cyclopentadec-2-en-1-one Chemical compound O=C1CCCCCCCCCCCCC=C1 LLWGDNREPDWSRL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 17
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 241000402754 Erythranthe moschata Species 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- BIKRAVWBNXPMMM-UHFFFAOYSA-N bicyclo[13.1.0]hexadecan-14-one Chemical compound O=C1CCCCCCCCCCCCC2CC12 BIKRAVWBNXPMMM-UHFFFAOYSA-N 0.000 abstract 2
- 240000002505 Pogostemon cablin Species 0.000 abstract 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 1
- GOTIICCWNAPLMN-UHFFFAOYSA-M trimethylsulfanium;bromide Chemical compound [Br-].C[S+](C)C GOTIICCWNAPLMN-UHFFFAOYSA-M 0.000 abstract 1
- 239000002537 cosmetic Substances 0.000 description 13
- 239000003599 detergent Substances 0.000 description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- 229910000104 sodium hydride Inorganic materials 0.000 description 5
- 239000012312 sodium hydride Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000002781 deodorant agent Substances 0.000 description 4
- 238000004851 dishwashing Methods 0.000 description 4
- -1 epoxide compound Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 239000000645 desinfectant Substances 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 238000005888 cyclopropanation reaction Methods 0.000 description 2
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 235000013355 food flavoring agent Nutrition 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- 239000002453 shampoo Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BPLKQGGAXWRFOE-UHFFFAOYSA-M trimethylsulfoxonium iodide Chemical compound [I-].C[S+](C)(C)=O BPLKQGGAXWRFOE-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241001237961 Amanita rubescens Species 0.000 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- 244000179970 Monarda didyma Species 0.000 description 1
- 235000010672 Monarda didyma Nutrition 0.000 description 1
- ALHUZKCOMYUFRB-OAHLLOKOSA-N Muscone Chemical compound C[C@@H]1CCCCCCCCCCCCC(=O)C1 ALHUZKCOMYUFRB-OAHLLOKOSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002386 air freshener Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007934 lip balm Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000002324 mouth wash Substances 0.000 description 1
- 229940051866 mouthwash Drugs 0.000 description 1
- ALHUZKCOMYUFRB-UHFFFAOYSA-N muskone Natural products CC1CCCCCCCCCCCCC(=O)C1 ALHUZKCOMYUFRB-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Abstract
Description
この発明は、化２ This invention is
各種化粧品類、防臭剤、室内芳香剤、消毒剤、殺虫剤等の保健衛生材料類、漂白剤、ソフトナー、食器洗い用洗剤、洗濯用洗剤等の賦香剤として絶えず新しい基調香気が求められている。また一方で、保留剤としてその力強いムスク様香気を有する化合物であるニトロムスクの例のように、近年使用が限定される化合物が見られる。しかしながら、ニトロムスクを欠いた調合品では、出来上がる香りに限界があり、市場から要請される嗜好性の有る香りとして答えるには十分ではない。そこで、新しい香気を有した香りや、従来の組成物に少量添加するだけで、一段と香りに動物的な力強さ、拡散性、持続性及び又は天然らしさを強化することができる新しい化合物の開発が要望されてきている。 New basic fragrances are constantly being sought as flavoring agents for various cosmetics, deodorants, indoor fragrances, disinfectants, insecticides, and other health and hygiene materials, bleaching agents, softeners, dishwashing detergents and laundry detergents. Yes. On the other hand, there are compounds that have been limited in use in recent years, such as nitromusk, which is a compound having a strong musk-like aroma as a retention agent. However, the preparation lacking nitromusk has a limit in the aroma that can be produced, and it is not enough to answer as a tasteful aroma required by the market. Therefore, the development of new fragrances and new compounds that can further enhance animal strength, diffusivity, sustainability and naturalness by adding a small amount to a conventional composition. Has been requested.
キラルなビシクロ［１３.１.０］ヘキサデカ−２−オンを天然型ムスコンの合成のための原料として用いることは従来公知である。そのため、ラセミ体である本化合物のうち一方の光学活性体を製造する方法として、唯一、エノンをホモキラルなケタールに転換後、ジヨードメタンを亜鉛−銅触媒の存在下にＤＭＳＯ溶媒中でナトリウムハイドライドとを作用させるケイス・エイ・ネルソン（Ｋｅｉｔｈ
Ａ Ｎｅｌｓｏｎ）らの方法があるのみであった（ジャーナル・オブ・アメリカン・ケミカル・ソサイエティー；１９９３年、１１５巻、１５９３−１５９４頁）。しかしながら、この方法は多量の亜鉛−銅触媒を必要とするうえ、発火の危険性の高いナトリウムハイドライドを使用することやジヨードメタンをこれも過剰に使用するもので、工業的なビシクロ［１３.１.０］ヘキサデカ−２−オンの製造法としては満足のいくものではない。
比較的最近、構造は本化合物と同じではないが比較的類似した化合物に対し、ＤＭＳＯ溶媒中でナトリウムハイドライドとトリメチルオキソスルフォニウム アイオダイドとをエノンに直接作用させる方法がユージーン・エイ・マーシュ等（Ｅｕｇｅｎｅ
Ａ Ｍａｓｈ）らによって報告されている（ジャーナル・オブ・オーガニック・ケミストリー；１９９７年、６２巻、８５１３−８５２１頁）。しかしながら、この方法は前述のケイス・エイ・ネルソン（Ｋｅｉｔｈ
Ａ Ｎｅｌｓｏｎ）らの方法によってホモキラルなケタールとし、あらかじめ光学活性なシクロプロパン化後、さらにもう一つのシクロプロパン化を実行する際に採用される方法であることや、発火の危険性の高いナトリウムハイドライドを使用すること、およびトリメチルオキソスルフォニウムブロマイドにくらべ高価なトリメチルオキソスルフォニウムアイオダイドを使用している点で、工業的なビシクロ［１３.１.０］ヘキサデカ−２−オンの製造法としては満足ではない。
The use of chiral bicyclo [13.1.0] hexadec-2-one as a raw material for the synthesis of natural muscone is conventionally known. Therefore, the only method for producing one of the racemic optically active compounds is to convert enone to a homochiral ketal, and then diiodomethane with sodium hydride in DMSO solvent in the presence of zinc-copper catalyst. Keith A. Nelson (Keith)
A Nelson et al. (Journal of American Chemical Society; 1993, 115, 1593-1594). However, this method requires a large amount of zinc-copper catalyst, uses sodium hydride, which has a high risk of ignition, and excessively uses diiodomethane, which is an industrial bicyclo [13.1. 0] The process for producing hexadec-2-one is not satisfactory.
Relatively recently, a method in which sodium hydride and trimethyloxosulfonium iodide directly act on enone in a DMSO solvent for a compound that is not the same as the present compound but relatively similar is disclosed in Eugene A. Marsh et al. Eugene
A Mash) et al. (Journal of Organic Chemistry; 1997, 62, 8513-8521). However, this method is not limited to the aforementioned Keith A. Nelson.
A Nelson) is used to form a homochiral ketal, which is pre-optically active cyclopropanation followed by another cyclopropanation, and sodium hydride with high risk of ignition. And the use of trimethyloxosulfonium iodide, which is more expensive than trimethyloxosulfonium bromide, for industrial production of bicyclo [13.1.0] hexadec-2-one Not as satisfied.
又、ビシクロ［１３.１.０］ヘキサデカ−２−オンが天然物中に極微量検出されたとする山口 功等による報告があるが（東京家政大学研究紀要２、自然科学、１９９７年、３７巻、１１５−１２０頁）、ビシクロ［１３.１.０］ヘキサデカ−２−オンが芳香を有することも、これが各種化粧品類、防臭剤、室内芳香剤、消毒剤、殺虫剤等の保健衛生材料類、漂白剤、ソフトナー、食器洗い用洗剤、洗濯用洗剤等の賦香剤として用いられるという記載もない。
ニトロムスクに代わり得る、従来の香料組成物に少量添加するだけで、香りに動物的な力強さ、拡散性、持続性及び又は天然らしさを強化し、芳香製品の芳香を改良又は増強することのできる芳香化合物の新しい製造方法を提供する。又、ニトロムスクに変わる、新しい香気を有し、従来の組成物に少量添加するだけで、一段と香りに動物的な力強さ、拡散性、持続性及び又は天然らしさを強化することができる新しい香料組成物を提供する。 It can replace nitromusk and can be added to conventional fragrance compositions in small amounts to enhance animal strength, diffusivity, persistence and / or naturalness to the scent and improve or enhance the fragrance of the fragrance product. Provided is a new method for producing an aromatic compound. Also, a new fragrance that has a new scent that replaces nitromusk and can be further enhanced in animal strength, diffusivity, persistence and / or naturalness by adding a small amount to a conventional composition. A composition is provided.
本発明者らは、上記のような課題に応えるべく鋭意研究を行った結果、ＤＭＳＯなどの有機溶媒に懸濁／溶解したソディウムハイドライド、カリウムターシャリーブトキサイド及びソディウムメトキサイドから選ばれる少なくとも一種の塩基にトリメチルスルフォキソニウムブロマイドを加えて、２−シクロペンタデセン−１−オンと、反応させることによって化３で示されるビシクロ[１３．１．０]ヘキサデカ−２−オン As a result of diligent research to respond to the above problems, the present inventors have found that at least one kind selected from sodium hydride, potassium tertiary butoxide and sodium methoxide suspended / dissolved in an organic solvent such as DMSO. Bicyclo [13.1.0] hexadec-2-one represented by Chemical formula 3 is prepared by adding trimethylsulfoxonium bromide to the base and reacting with 2-cyclopentadecene-1-one.
を容易に製造できることを見出した。またこの化合物がパチュリ様香気を伴った動物的なムスク香を有していることを見出すとともに、それらの香気的特徴だけでなく香気成分として含有せしめた香料組成物として用いる時、芳香組成物の香りに動物的な力強さ、拡散性、持続性を顕著に強化することを見出し、これらの知見に基づいて本発明を完成した。即ち、本発明は、ビシクロ[１３．１．０]ヘキサデカ−２−オンの簡便な製造法であり、ビシクロ[１３．１．０]ヘキサデカ−２−オンを賦香成分として含有する香料組成物であり、又、ビシクロ[１３．１．０]ヘキサデカ−２−オンを添加することにより、フレーグランス製品の基礎香気に動物的な力強さ、拡散性、持続性及び又は天然らしさを強化する、芳香製品の香気を改良又は増強する方法である。 It was found that can be easily manufactured. In addition, it is found that this compound has an animal-like musk fragrance with a patchouli-like fragrance, and when used as a fragrance composition incorporated as a fragrance component as well as their fragrance characteristics, It was found that animal strength, diffusibility, and sustainability were remarkably enhanced in aroma, and the present invention was completed based on these findings. That is, the present invention is a simple process for producing bicyclo [13.1.0] hexadec-2-one, and a fragrance composition containing bicyclo [13.1.0] hexadec-2-one as a flavoring component. In addition, the addition of bicyclo [13.1.0] hexadec-2-one enhances animal strength, diffusivity, persistence and / or naturalness to the basic fragrance of fragrance products A method for improving or enhancing the fragrance of a fragrance product.
本発明を実施することによって、従来簡便に調製する方法が知られていなかった、ビシクロ[１３．１．０]ヘキサデカ−２−オンがケトンのエポキシ化を抑えて、極めて容易且つ大量に製造でき、かくして得られるビシクロ[１３．１．０]ヘキサデカ−２−オンは、ニトロムスクに変わる、新しい香気を有し、従来の組成物に少量添加するだけで、一段と香りに動物的な力強さ、拡散性、持続性及び又は天然らしさを強化することができる新しい香料組成物の提供が可能となる。 By carrying out the present invention, bicyclo [13.1.0] hexadec-2-one, which has not been conventionally known for its simple preparation method, can be produced very easily and in large quantities by suppressing the epoxidation of ketones. The bicyclo [13.1.0] hexadec-2-one thus obtained has a new scent that changes to nitromusk, and can be added to a conventional composition in a small amount to further enhance the scent of animal strength, It becomes possible to provide a new fragrance composition capable of enhancing diffusibility, persistence and / or naturalness.
一般に、二重結合にトリメチルスルフォキソニウムブロマイド（アイオダイド）から得られるイリドを作用させると、ケトンからはエポキサイド化合物が得られ、炭素炭素二重結合からはシクロプロパン環化合物が得られる。
本発明において、適量の有機溶媒、例えばジメチルスルフォキサイド（ＤＭＳＯ）、イミダゾリジノン（ＤＭＩ）、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン（ＤＢＵ）などから選ばれる一つの有機溶媒に懸濁又は溶解させた化学量論量以上のカリウムターシャリーブトキサイド又はソディウムメトキサイド塩基の存在下に、１．０〜３．０等量のトリメチルスルフォキソニウムブロマイドを数回に分けて攪拌しながら加え、反応器中でイリドを発生させ、これに２−シクロペンタデセン−１−オンを凡そ４０℃以下、通常室温に保ちながら添加することでケトンのエポキシ化を抑え、二重結合へのメチレン基の導入を優先することができる。
In general, when an ylide obtained from trimethylsulfoxonium bromide (iodide) is allowed to act on a double bond, an epoxide compound is obtained from a ketone, and a cyclopropane ring compound is obtained from a carbon-carbon double bond.
In the present invention, an appropriate amount of an organic solvent such as dimethyl sulfoxide (DMSO), imidazolidinone (DMI), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) or the like is selected. Several times 1.0-3.0 equivalents of trimethylsulfoxonium bromide in the presence of a stoichiometric or higher amount of potassium tertiary butoxide or sodium methoxide base suspended or dissolved in two organic solvents In order to suppress the epoxidation of the ketone by adding 2-cyclopentadecen-1-one to the reactor while stirring at about 40 ° C. or lower, usually at room temperature. Preference can be given to the introduction of a methylene group into the double bond.
本発明を実施するに当って、出発物質である２−シクロペンタデセン−１−オンは、特開昭５１−４８６３５号公報に記載されており、又、特許公開公報２００１−２２６３０６に記載の方法により得られる混合物 ２（３）−シクロペンタデセン−１−オンも用いることができる。 In practicing the present invention, 2-cyclopentadecene-1-one as a starting material is described in JP-A No. 51-48635, and a method described in JP-A-2001-226306. It is also possible to use a mixture 2 (3) -cyclopentadecene-1-one obtained by
本発明においては、得られたビシクロ[１３．１．０]ヘキサデカ−２−オンを、石鹸、シャンプー、リンス等の化粧品類、洗毛料、養毛料等の頭髪用化粧品類、クリーム、化粧水、オーデコロン、パック等の基礎化粧品類、おしろい、ファンデーション、頬紅等のメークアップ化粧品類、香水等の芳香化粧品類、日焼け、日焼け止め化粧品、口紅、リップクリーム等の口唇化粧品類、歯磨き、マウスウォッシュ等の口腔化粧品類、浴用化粧品等各種化粧品類、防臭剤、室内芳香剤等の芳香剤類、消毒剤、殺虫剤等の保健衛生材料類、漂白剤、ソフトナー、食器洗い用洗剤又は洗濯用洗剤等に使用される通常の賦香剤組成物に適当量含有せしめても良く、或いはこれらの各種賦香剤が添加された各種化粧品類、防臭剤、室内芳香剤、保健衛生材料類、漂白剤、ソフトナー、食器洗い用洗剤、洗濯用洗剤等に直接添加混合してもよい。 In the present invention, the obtained bicyclo [13.1.0] hexadec-2-one is used for cosmetics such as soaps, shampoos and rinses, cosmetics for hair such as hair wash, hair conditioner, cream, lotion, Basic cosmetics such as eau de cologne, packs, makeup cosmetics such as funny, foundation, blusher, aromatic cosmetics such as perfume, lip cosmetics such as tanning, sunscreen cosmetics, lipstick, lip balm, toothpaste, mouthwash, etc. For various cosmetics such as oral cosmetics, bath cosmetics, deodorants, indoor air fresheners, sanitary materials such as disinfectants, insecticides, bleaching agents, softeners, dishwashing detergents or laundry detergents It may be contained in an appropriate amount in the normal fragrance composition used, or various cosmetics, deodorants, indoor fragrances, health and hygiene materials to which these various fragrances are added. S, bleaches, softeners, dishwashing detergents, may be added and mixed directly into laundry detergent or the like.
上記通常の賦香剤組成物が用いられる香りのタイプとしては、ミュゲタイプ、ムスクローズタイプ、グリーンフローラルタイプ、ベルガッモットタイプ等に、その用途はソープ用、芳香剤等何れに使用してもよく、これらにビシクロ[１３．１．０]ヘキサデカ−２−オンを適量添加、含有せしめることにより、既存香料の香りに、深み、力強さ、天然らしさ、拡散性及び又は甘みを与える新しい香りを発揮する。又、ジャスミンタイプ様芳香剤、フローラルブーケ等に添加したときには、香りに深みと拡散性を与え、且つそれぞれの持つ香りに一層天然らしさを強くする。
その添加料は、通常の賦香剤組成物中に０．１〜１００重量％含有せしめる。
As a fragrance type in which the above-mentioned ordinary fragrance composition is used, it can be used for muge type, musculo type, green floral type, bergamot type, etc. Well, adding a proper amount of bicyclo [13.1.0] hexadeca-2-one to these, and adding them to the fragrance of the existing fragrance, a new fragrance that gives depth, strength, naturalness, diffusibility and / or sweetness Demonstrate. Moreover, when added to a jasmine type-like fragrance, floral bouquet or the like, the fragrance is given depth and diffusibility, and the naturalness of each fragrance is further enhanced.
The additive is contained in an ordinary fragrance composition in an amount of 0.1 to 100% by weight.
以下、実施例を用いて本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。
実施例1
ビシクロ［１３.１.０］ヘキサデカ−２−オン（１）の製造
原料として用いる２−シクロペンタデセン−１−オンの合成法は特に限定しないが、たとえば特許公開公報２００１−２２６３０６に記載の方法により得られる混合物 ２（３）−シクロペンタデセン−１−オンも用いることができるので、ここでは特許公開公報２００１−２２６３０６に記載の方法により得られた混合物としての２（３）−シクロペンタデセン−１−オンを使用する例を記す。
EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to these.
Example 1
Production of bicyclo [13.1.0] hexadec-2-one (1) The method for synthesizing 2-cyclopentadecene-1-one used as a raw material is not particularly limited, but for example, Patent Publication 2001-226306. 2 (3) -cyclopentadecene-1-one obtained by the method described in JP-A-2001-226306 can be used. An example using -cyclopentadecene-1-one will be described.
還流冷却器、温度計、攪拌機を備えた１Ｌの四頚フラスコに３６０ｍＬのジメチルスルフォキサイド（ＤＭＳＯ）を入れ、室温でソジウムメトキサイドの２８％メタノール溶液５４ｇ（０．２５×１．１ｍｏｌ）を加える。３０分攪拌後、５０ｇのトリメチルスルホキソニウムブロマイド（ＴＭＳＯＢ、０．２５×１．５ｍｏｌ）を１５分間隔で、３回に分けて加える。加えた後さらに３０分攪拌する。これに、特許公開公報２００１−２２６３０６に記載の方法により得られた蒸留により得られた２（３）−シクロペンタデセン−１−オンの混合物の５６ｇ（０．２５ｍｏｌ、ただしガスクロチャートより純度換算すると２−シクロペンタデセン−１−オンとしては０．１７ｍｏｌ）を滴下して加える。滴下中僅かに発熱するので、水浴により４０度以下に保つ。さらに同温度で１時間攪拌を継続した後、反応液を３００ｍＬの氷水に攪拌しつつ投入する。これを２００ｍＬのイソプロピルエーテル（ＩＰＥ）で３回抽出する。ＩＰＥ層を２０ｍＬの５％塩酸で洗浄後、５００ｍＬの飽和食塩水で３回洗浄して中性とする。有機層を乾燥剤で乾燥した後濃縮すると、５８ｇの燈黄色油状物が得られる。 In a 1 L four-necked flask equipped with a reflux condenser, thermometer, and stirrer, 360 mL of dimethyl sulfoxide (DMSO) was placed, and 54 g (0.25 × 1.1 mol) of a 28% methanol solution of sodium methoxide at room temperature. ). After stirring for 30 minutes, 50 g of trimethylsulfoxonium bromide (TMSOB, 0.25 × 1.5 mol) is added in three portions at 15 minute intervals. Stir for another 30 minutes after addition. To this, 56 g (0.25 mol of a mixture of 2 (3) -cyclopentadecen-1-one obtained by distillation obtained by the method described in Patent Publication 2001-226306 (however, when converted to purity from a gas chromatograph) 0.17 mol) is added dropwise as 2-cyclopentadecen-1-one. Since it generates heat slightly during the dropping, it is kept at 40 ° C. or less with a water bath. Further, stirring is continued for 1 hour at the same temperature, and then the reaction solution is added to 300 mL of ice water while stirring. This is extracted three times with 200 mL of isopropyl ether (IPE). The IPE layer is washed with 20 mL of 5% hydrochloric acid and then neutralized by washing with 500 mL of saturated saline three times. The organic layer is dried with a desiccant and then concentrated to give 58 g of a pale yellow oil.
これを減圧下（３ｍｍＨｇ）に蒸留して、１３７℃から１４３℃の溜分として３６．９ｇの結晶物を得た。この結晶物はガスクロマトグラムによる純度測定により９４．４％の面積百分率を示すとともに、ＧＣ−ＭＳ測定結果から、得られた結晶の主成分がビシクロ［１３.１.０］ヘキサデカ−２−オン（１）の文献値（非特許文献１）によく一致することを確認した。また、ここで得られた主成分以外のガスクロマトグラムピークには、カルボニル基だけへのイリドの付加生成物は見当たらなかった。 This was distilled under reduced pressure (3 mmHg) to obtain 36.9 g of crystal as a fraction at 137 ° C to 143 ° C. This crystallized product shows an area percentage of 94.4% by gas chromatogram purity measurement, and from the results of GC-MS measurement, the main component of the obtained crystal is bicyclo [13.1.0] hexadec-2-one ( It was confirmed that it well matched the literature value of 1) (Non-patent Literature 1). In addition, in the gas chromatogram peaks other than the main component obtained here, no addition product of ylide to the carbonyl group was found.
ＧＣ−ＭＳ；ｍ/ｚ（相対値）２３６（５）、１２５（９）、１０９（１８）、９７（２８）、７２（９５）、４１（１００）。
更に、これをトルエン溶媒によるシリカゲル−カラムクロマトで精製し、ガスクロマトグラムによる純度測定で９９％の白色結晶２９．９ｇを得た後、その結晶のNMR、ＩＲ測定を行いビシクロ［１３.１.０］ヘキサデカ−２−オン（１）であることを確認した。
１Ｈ ＮＭＲ（ＣＤＣｌ３）；δ ０．６６−０．９２（３，ｍ）、１．０７−１．６２（２０，ｍ）、１．６８−１．７７（１，ｍ）、１．７９−２．０１（２，ｍ）、２．３６−２．７１（２，ｍ）。
ＩＲ（ＣＨＣｌ３）；ｃｍ−１２９２８、２８６０、１６９８、７５６。
GC-MS; m / z (relative value) 236 (5), 125 (9), 109 (18), 97 (28), 72 (95), 41 (100).
Further, this was purified by silica gel column chromatography with a toluene solvent to obtain 29.9 g of 99% white crystals by gas chromatogram purity measurement. Then, the crystals were subjected to NMR and IR measurements to perform bicyclo [13.1.0. It was confirmed to be hexadec-2-one (1).
1 H NMR (CDCl 3 ); δ 0.66-0.92 (3, m), 1.07-1.62 (20, m), 1.68-1.77 (1, m), 1. 79-2.01 (2, m), 2.36-2.71 (2, m).
IR (CHCl 3 ); cm −1 2928, 2860, 1698, 756.
表１に示した基本組成を有するミュゲタイプ香料を処方し（対照区）、これに上に得られたビシクロ［１３.１.０］ヘキサデカ−２−オン（１）を０．１部（試料Ａ）、1部（試料Ｂ）、１０部（試料Ｃ）夫々添加混合して、常法通り室内芳香剤用組成物を調製した。これらを専門パネラー１０名に官能評価をさせ、得られた総合評価結果を表２に示した。 A Muguet-type fragrance having the basic composition shown in Table 1 was formulated (control group), and 0.1 parts (sample) of bicyclo [13.1.0] hexadec-2-one (1) obtained above was prepared. A), 1 part (sample B), and 10 parts (sample C) were added and mixed to prepare a composition for indoor fragrance as usual. These two were subjected to sensory evaluation by 10 professional panelists, and the obtained comprehensive evaluation results are shown in Table 2.
実施例２
表３に示した基本組成を有するムスクローズ香料を処方し（対照区）、これにビシクロ［１３.１.０］ヘキサデカ−２−オン（１）を０．１部（試料Ａ）、１０部（試料Ｂ）、１００部（試料Ｃ）夫々添加混合して、ムスク調香料用ベースを調製した。これらを専門パネラー１０名に官能評価をさせ、得られた総合評価結果を表４に示した。
Example 2
Musculous fragrance having the basic composition shown in Table 3 was formulated (control group), and 0.1 parts (sample A), 10 parts of bicyclo [13.1.0] hexadec-2-one (1) was added thereto. (Sample B) and 100 parts (Sample C) were added and mixed to prepare a base for musk flavor. These four were subjected to sensory evaluation by 10 professional panelists, and the obtained comprehensive evaluation results are shown in Table 4.
実施例３
表５に示した基本組成を有するグリーンフローラル香料を処方し（対照区）、これにビシクロ［１３.１.０］ヘキサデカ−２−オン（１）を５０部添加混合して、シャンプー用香料組成物を調製した。
このものの香りは、対照のものに比べて自然でしっかりしたグリーンな感じが強調された。
Example 3
A green floral fragrance having the basic composition shown in Table 5 was formulated (control group), and 50 parts of bicyclo [13.1.0] hexadec-2-one (1) was added to and mixed with the fragrance composition for shampoo. A product was prepared.
The scent of this product emphasized a natural, firm green feeling compared to the control.
Claims (4)
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| US20150057207A1 (en) * | 2013-08-22 | 2015-02-26 | International Flavors & Fragrances Inc. | Novel organoleptic compounds |
| EP2842941A4 (en) * | 2012-04-24 | 2015-12-23 | Kureha Corp | Method for producing trimethylsulfoxonium bromide and temperature control method for reaction system producing trimethylsulfoxonium bromide |
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| JPH029835A (en) * | 1988-03-11 | 1990-01-12 | Kuraray Co Ltd | Preparation of bicyclohumulenone |
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